CN1970670B - Adhesive containing block copolymers - Google Patents
Adhesive containing block copolymers Download PDFInfo
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- CN1970670B CN1970670B CN2006101603340A CN200610160334A CN1970670B CN 1970670 B CN1970670 B CN 1970670B CN 2006101603340 A CN2006101603340 A CN 2006101603340A CN 200610160334 A CN200610160334 A CN 200610160334A CN 1970670 B CN1970670 B CN 1970670B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
Abstract
The invention relates to an adhesive containing block copolymers. Hot melt adhesive compositions containing a polystyrene-polyisoprene/polybutadiene-polystyrene block copolymer and its use in the manufacture of disposable absorbent articles. The adhesive comprises a thermoplastic polystyrene-polyisoprene/polybutadiene- polystyrene block copolymer having a styrene content of at least 25 wt % and a diblock percentage of less than 30 %, a second thermoplastic block copolymer and a tackifier.
Description
Technical field
The present invention relates to adhesive compound, more particularly, relate to the hot melt adhesive that is specially adapted to make elasticity connection tackiness agent or is used for Stretch material.This tackiness agent comprises PS-isoprene/butadiene multipolymer-polystyrene block copolymer.
Background technology
The hot melt adhesive that is in molten state be applied on the base material and make it the cooling with this adhesive layer that hardens.This type tackiness agent has been widely used in during various commercial and industrials use, like product assembling and packing, and has been widely used in and makes baby' diaper and adult incontinence products in the non-woven industry, under two kinds of situation, all is connected tackiness agent as sqtructural adhesive with elasticity.In these were used, tackiness agent was applied at least a polyolefine nonwoven substrates, at least a spandex fiber such as Spandex and/or at least a polyolefin film, so that bond together these base materials.
The various materials owing in disposable use goods, will in the very big condition and range of difference, bond have worked out and have been applicable to the various tackiness agent of making disposable use goods.This point is especially true in elasticity connection and laminate structures.That structure need have is controlled, that viscosity is lower, the open hour long and cohesive strength is enough to keep layer to close the tackiness agent of sheet mechanics globality.But, in order to be bonded to resilient material on the base material, be with different tackiness agent with high creep resistance, can not move or become part or all of disengagement under stress to guarantee resilient material with respect to substrate surface.Have the sole binder that makes tackiness agent can be applicable to that laminate and elastic bonding are used and be called the multi-usage tackiness agent.
Although traditionally comprising that the hot melt adhesive that calls the multiple purpose thermosol stick is used for non-woven application, still need use the tackiness agent that preparation more effectively bonds together the base material of some type for some is final.The present invention has satisfied this requirement.
Summary of the invention
Have been found that; PS-isoprene/butadiene multipolymer-polystyrene block copolymer (this paper is abbreviated as the S-I/B-S segmented copolymer); As the base polymer in the melt viscosity agent prescription time, the tackiness agent that is specially adapted to make disposable use goods is provided.The content of the end block styrene of S-I/B-S segmented copolymer at least 25 weight % and diblock percentage ratio less than about 30%.In one embodiment, the diblock percentage ratio of S-I/B-S segmented copolymer is less than about 25%.In another embodiment, the content of the diblock of S-I/B-S segmented copolymer is less than about 20%.Mid-block is formed by isoprene and divinyl random copolymerization.But being applicable to, this tackiness agent does that elasticity connects tackiness agent or the tackiness agent of the oriented film that closes as Stretch material such as Stretchable nonwoven fabric or with another kind of nonwoven material or other material layer.
Hot melt adhesive provided by the invention comprises styrene content at least 25 weight % and diblock percentage ratio less than about 30% thermoplasticity S-I/B-S segmented copolymer, second thermoplastic elastomer and tackifying resin; And, preferably can also comprise attenuant, wax and other conventional hot melt tackiness agent additive.
The target of an embodiment is the tackiness agent that comprises following component among the present invention: the weight with adhesive compound is that benchmark calculates; 0.5 weight %～about 18 weight % thermoplasticity S-I/B-S segmented copolymers, about 30～80 weight % tackifying resins; The second different thermoplastic segmented copolymer of the about 30 weight % of maximum consumption, the wax of the liquid plasticizer of about at the most 25 weight % and about at the most 25 weight %.
In a preferred embodiment, target of the present invention is the tackiness agent that comprises following component: about 5 weight %～about 18 weight % styrene contents at least 25 weight % and diblock percentage ratio are less than about 30% thermoplasticity S-I/B-S segmented copolymer, about 10～about 30 weight %, second different segmented copolymers and about 30～about 70 weight % tackifying resins.Liquid plasticizer and maximum consumption that preferred adhesive compound also will randomly comprise the about 25 weight % of maximum consumption are the wax of about 5 weight %.This embodiment is specially adapted to elasticity and connects application.
In a further preferred embodiment, target of the present invention is the tackiness agent that comprises following component: cinnamic content at least 25 weight % of about 0.5 weight %～about 18 weight % and diblock percentage ratio are less than about 30% S-I/B-S segmented copolymer and about 5～about 70 weight % tackifying resins.Liquid plasticizer and maximum consumption that preferred adhesive compound also will randomly comprise the second different segmented copolymers of the about 30 weight % of maximum consumption, the about 20 weight % of maximum consumption are the wax of about 5 weight %.This embodiment is particularly suitable for making the flexible laminate sheet.
In also having a preferred embodiment; Target of the present invention is the tackiness agent that comprises following component: about 0.5 weight %～about 18 weight % styrene contents at least 30 weight % and diblock percentage ratio is less than 25% thermoplasticity S-I/B-S segmented copolymer, about 5～about 30 weight %, second different segmented copolymers and about 30～about 70 weight % tackifying resins.Preferred adhesive compound also will randomly comprise the liquid plasticizer of the about 20 weight % of maximum consumption and the wax of the about 5 weight % of maximum consumption.
Adhesive compound of the present invention has good cohesive strength when being used for multiple application.These tackiness agent have good cohesive strength as sqtructural adhesive the time; And be used for making the goods that comprise the elastic region as elasticity connection tackiness agent; As when comprising the disposable absorbent garment of one or more elasticity ring sets that contact with the leg or the waist of wearer, has good creep property.
The present invention also provides the goods that comprise hot melt adhesive, and said hot melt adhesive comprises about at the most 18 weight % styrene contents at least 25 weight % and diblock percentage ratio less than 30% thermoplasticity S-I/B-S segmented copolymer.Goods generally will comprise at least a base material.The present invention also comprises disposable absorbing products, comprises disposable absorbent garment, comprises those that contain at least a elastic substrate or at least a Stretch material.
Embodiment
The document that this paper quoted is included in totally that this is for reference.
The present invention provides the hot melt adhesive composition that comprises segmented copolymer, and said segmented copolymer contains the diblock component of isoprene/butadiene mid-block and certain content.Specifically, the present invention provides and comprises styrene content at least 25 weight % and the diblock percentage ratio hot melt adhesive less than 30% thermoplasticity S-I/B-S segmented copolymer.Hot melt adhesive of the present invention can be used as sqtructural adhesive and is used between Stretch material and second base material, forming elasticity and is connected bonding and formation construction bonds; Thereby make this tackiness agent be highly suitable for making nonwoven disposable and use goods, like baby' diaper, training pant and adult incontinence products.
One of required most important performance was a creep property during elasticity connected.In this connection, require tackiness agent to have good toughness.Tackiness agent of the present invention satisfies elasticity and connects the application strict demand required with other application.Therefore this tackiness agent is specially adapted to make elastic nonwovens and makes baby' diaper, training pant, adult-incontinence articles or underwear etc.Compsn of the present invention is mixed with superior bond strengths rendering with less polymer content in prescription, thereby has produced the high-efficiency adhesion agent system.
Hot melt adhesive of the present invention comprise S-I/B-S segmented copolymer, the second different thermoplastic elastomerics, tackifying resin and, preferably, also have liquid plasticity with, randomly, wax.Be different from less than 30% S-I/B-S segmented copolymer and another kind with the styrene content at least 25 weight % of lower aq (about 18 weight % or still less) and diblock percentage ratio; It promptly not the thermoplastic block polymkeric substance (this paper also is referred to as " the second different segmented copolymers ") of S-I/B-S segmented copolymer; Make up, but obtain being applicable to that elasticity connects the high-performance hot melt adhesive that closes sheet with tensile layer.
Be used for putting into practice SIBS segmented copolymer of the present invention and be styrene content at least 25 weight % and diblock percentage ratio less than polystyrene-poly isoprene/polyhutadiene-PS (S-I/B-S) segmented copolymer of 30%.The melt flow index that records with the ISO1133 method be 6～11g/10min (200 ℃, 5kg).This base polymer can be by publishing U.S. Patent application 2004/0167292 described method manufacturing and can be available from Kraton Polymer US.
Gluing among the present invention also will comprise at least a segmented copolymer that generally is configured as A-B-A; Wherein polymer ends block A is the non-elastomer polymer section; It is as homopolymer; Second-order transition temperature is higher than about 20 ℃, and elastomer polymer interlude B is then derived from can part or basic hydrogenant isoprene, divinyl or iso-butylene, or their mixture.For the purpose of convenient and clear, this paper is called the second different block copolymer component in the tackiness agent of the present invention to this based block copolymer.That this base polymer comprises is linear, radiation shape and star block copolymer.
Inelastic body end block A can comprise the homopolymer and the multipolymer of vinyl monomer and Acrylic Acid Monomer; Said vinyl monomer such as vinyl-arene, vinyl pyridine, halogen ethene, vinyl carboxylate, said Acrylic Acid Monomer such as vinyl cyanide, methacrylonitrile, propenoate etc.Monovinylarene especially comprises those of benzene series row, like vinylbenzene, Vinyl toluene, vinyl-dimethyl benzene and vinyl xylene, ethyl vinyl benzene and two ring mono-vinyl compounds, like vinyl naphthalene and analogue.Other non-elastomer polymer block can be derived from terminal olefin, alkylene oxide, acetal, ammonia ester etc.Optimization styrene.
The elastomerics mid-block B component that constitutes the thermoplastic elastomer copolymer rest part is derived from isoprene or divinyl, and they can be hydrogenated, and like U.S. patent 3,700,633 is said.The hydrogenation of divinyl can part or complete basically.Selected condition can be used to, for example, and hydrogenation elasticity butadiene block and do not change the vinyl aromatic polymer block.Can select other condition to come basically equably along polymer chain hydrogenation, elastomerics and inelastic body block all are hydrogenated to essentially identical degree, no matter be part or basic hydrogenation fully.Preferred hydropolymer, purpose is the degraded that reduces during processing, for higher molecular weight polymer, this is more serious problem.
Adhesive compound of the present invention will usually comprise the A-B-A segmented copolymer of about at the most 30 weight %, more typically, and about at the most 20 weight %.Instance comprises styrene-isoprene-phenylethene (SIS), styrene-butadiene-styrene (SBS), vinylbenzene-iso-butylene-vinylbenzene (SIBS), styrene-ethylene/butylene-styrene block copolymer (SEBS), and/or styrene-ethylene/propylene-styrene segmented copolymer (SEPS).
In adhesive compound, segmented copolymer, promptly the total amount of S-I/B-S and A-B-A segmented copolymer is generally at least about 13 weight % or more.
Tackiness agent of the present invention generally also will comprise the tackifier compatible with the thermoplastic elastomer mid-block.The typical amount of tackifier is about 5～about 70 weight %.In the prescription that is used for being laminated to Stretch material on the another kind of base material, the typical amount of tackifier will be about 30～70 weight %.Preferred ring-ball softening point is higher than about 25 ℃ tackifier.The tackifier that are suitable for comprise any compatible resin or their mixture, the natural or modified rosin like (1), for example, rosin, wood rosin, tall oil rosin, distillation rosin, staybelite, dimerization colophonium and polymerized rosin; (2) glyceryl ester and the pentaerythritol ester of natural or modified rosin are like the glyceryl ester of light wood rosin, the glyceryl ester of staybelite, the glyceryl ester of polymerized rosin, the pentaerythritol ester and the rosiny phenolic aldehyde-modification pentaerythritol ester of staybelite; (3) multipolymer of natural terpenes or terpolymer, for example, styrene/terpene and alpha-methyl styrene/terpenes; (4) press ASTM method E28, it is about 80～150 ℃ polyterpene resin that 58T records softening temperature; The polyterpene resin of back is generally by terpene hydrocarbon, as is called two ring monoterpene of firpene, under medium low temperature, processes having in the presence of the Friedel-Crafts catalyzer; Also comprise the hydrogenation polyterpene resin; (5) phenol aldehyde modified terpine resin and hydrogenated derivatives thereof, for example, the resin product that generates by two cyclic terpene alkene and the condensation of phenol in acidic medium; (6) ball-about 70～135 ℃ α-petroleum hydrocarbon resin of ring softening temperature; This resinoid of back is that the monomer polymerization of staple forms by alkene and diolefine; Also comprise Hydrogenated aliphatic α-petroleum hydrocarbon resin; (7) alicyclic petroleum hydrocarbon resin and hydrogenated derivatives thereof; And (8) aliphatic series/aromatics or cyclic aliphatic/aromatic copolymer and their hydrogenated derivatives.
The preferred tackifier that are applicable to this comprise polyterpene, aliphatic resin, cycloaliphatic resin and aliphatic series/aromatics or cyclic aliphatic/aromatic copolymer.More preferably aliphatic series and cycloaliphatic resin.Instance comprises the Wingtack 95 that is derived from Goodyear, be derived from the Eastotac H100R of Eastman Cheimcal Company and be derived from the ESCOREZ5600 of ExxonMobil Chemical Company.The desirability of concrete tackifier can be depending on used concrete elastomeric block copolymers with selection.
In addition, in tackiness agent, preferably be added to the end block tackifying resin of many about 30 weight %.After the tackiness agent cooling, end block tackifying resin mainly is present in the inelastic body block of thermoplastic elastomer.This resinoid representative is based on the basic aromatic resin of mixed C 9 petroleum distillate streams; As be derived from the material of Eastman Chemical Company; Or based on the resin of the pure or mix monomer of aromatic monomer stream, like the homopolymerization or the multipolymer of Vinyl toluene, vinylbenzene, alpha-methyl styrene, cumarone or indenes.Be preferably based on those of alpha-methyl styrene, can be available from Eastman Chemical Company, two article Kristalex by name and Plastolyn.If exist, the general consumption of then holding the block resin is about 1～about 30 weight %, preferably is less than about 20 weight %.
The tackifying resin that the interlude that preferred adhesive compound generally all will contain have an appointment 30～about 80 weight % and segmented copolymer is compatible and the compatible thermoplastic hydrocarbon tackifier of end block of about 5～about 30 weight % and segmented copolymer.
Can also exist in the tackiness agent mainly is aliphatics and the oil and other liquid diluent compatible with the thermoplastic elastomer mid-block.Compsn of the present invention generally will comprise the liquid plasticizer that consumption is less than about 25 weight %.Compsn of the present invention generally will comprise at least about 1 weight %, more typically, and at least about the liquid plasticizer of 5 weight %.Instance comprises softening agent, like paraffin and cycloalkanes petroleum oil, high refining no aromatic hydrocarbons paraffin and cycloalkanes food and the white oil MO of technical grade, and liquid tackifier, like the synthesizing liquid oligomer of polybutylenes, Vestolen PP 7052, polyterpene etc.The synthesizing series treated oil is the HV oligomer, and they are liquid forever monoolefine, medium isoparaffin or paraffin to HMW.Liquid plasticising or tackify thinner comprise polyterpene, as be derived from Goodyear Wingtack 10, be derived from Exxon Cheimcal based on C
5The Escorez 2520 of feeding stream.Other liquid diluent comprises the TR 301 LIR 50 that is derived from Kuraray, the polybutylenes that is derived from Amoco, and commodity are called Indopol.Most preferably Yellow Protopet 2A and Escorez 2520, i.e. C
5The combination of the polymkeric substance of oil feeding stream.
In addition, randomly, can also there be the wax of about at the most 5 weight %, like polyethylene wax.If use, then the amount of wax is generally at least about 2 weight %.
The maximum amount of oxidation inhibitor commonly used can be about 3 weight % in the rubber-based pressure-sensitive adhesive is produced.In suitable stablizer used herein or oxidation inhibitor, comprise high molecular weight hindered phenols and polyfunctionality phenol, like sulfur-bearing and phosphorous phenol.Hindered phenol is well-known to those skilled in the art, and the phenolic compound that can contain the space steric hindrance group of adjacent phenolic hydroxyl group is a characteristic.Especially at least one ortho position with respect to phenolic hydroxyl group is replaced by the tertiary butyl on phenyl ring.Typical hindered phenol comprises: 1,3, and 5-trimethylammonium 2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; Tetramethylolmethane base four-3 (3, the 5-di-tert-butyl-hydroxy phenyl)-propionic ester; 4,4 '-methylene-bis (2, the 6-tert.-butyl phenol); 4,4 '-sulphur two (the 6-tertiary butyl-neighbour-cresols); 2,6 di t butyl phenol; 6-(4-hydroxyphenoxy)-2, two (the n-octyl sulphur)-1,2 of 4-, 5-triazine; Two Octadecane bases 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester; 2-(n-octyl sulphur) ethyl 3,5-di-tert-butyl-4-hydroxybenzoic acid ester; With sorbyl alcohol six [3-(3, the 5-di-tert-butyl-hydroxy phenyl)-propionic ester].
Tackiness agent of the present invention will comprise about at the most 18 weight % styrene contents at least 25 weight % and diblock percentage ratio less than about 25% S-I/B-S segmented copolymer, another kind be selected from as; But be not limited to; The different segmented copolymers of the shape block copolymer of SIS, SBS, SEBS, SEPS, SIBS and their combination, tackifying resin and; Randomly, liquid plasticizer, wax or their combination.Weight with adhesive compound is benchmark; The typical amount of SIBS segmented copolymer is 0.5 weight %～about 18 weight %; The about at the most 20 weight % of typical amount of another kind of segmented copolymer, and the typical amount of tackifying resin is about 30～about 80 weight %.Tackiness agent can randomly also comprise the softening agent of the about 25 weight % of maximum consumption and the wax of the about 5 weight % of maximum consumption.
An embodiment is particularly suitable for being used to comprise the goods that Stretch material is a base material as sqtructural adhesive, like baby' diaper or adult incontinence product.Sqtructural adhesive comprises about 10～about 18 weight % styrene contents at least 25 weight % and diblock percentage ratio less than 30% SIBS segmented copolymer; The another kind of segmented copolymer of about 5～about 20 weight % is like SIS, SBS, SEBS, SEPS, SIBS and their combination; About 30～about 70 weight % tackifying resins; 0～25 weight % liquid plasticizer and 0～about 5 weight % waxes.
Another embodiment is particularly suitable for connecting tackiness agent as elasticity and is used for disposable goods.Elasticity connects tackiness agent and contains about 0.5～about 18 weight % styrene contents at least 25 weight % and diblock percentage ratio less than 30% SIBS segmented copolymer; Maximum consumption is the another kind of segmented copolymer of 20 weight %, like SBS, SEBS, SEPS, SIBS and their combination; About 5～about 70 weight % tackifying resins; 0～about 20 weight % liquid plasticizers and 0～about 5 weight % waxes.
Also having the target of an embodiment is the tackiness agent that comprises following component: about 0.5～about 18 weight % styrene contents at least 25 weight % and diblock percentage ratio are less than 25% S-I/B-S segmented copolymer; The another kind of segmented copolymer of about 5～about 20 weight % is like SBS, SEBS, SEPS, SIBS and their combination; About 30～about 70 weight % tackifying resins; 0～about 20 weight % liquid plasticizers and 0～about 5 weight % waxes.
Hot melt adhesive composition of the present invention can be used technology preparation known in the art.Exemplary steps comprises: in disposing the jacketed mixing kettle of rotor, preferably in jacketed heavy burden mixing tank, add about 20% oil or liquid diluent and all thermoplastic polymer and stablizers; Be raised to temperature the highest about 190 ℃ then.After thing to be mixed has melted, drop to 150～165 ℃ to temperature.Continue to mix and heat, at that time, infiltrate tackifying resin, wax and remaining thinner therein thoroughly, equably up to obtaining smooth uniform quality.
Tackiness agent can be applied on the needed base material with any method known in the art; Said method comprises; But be not limited to; Roller coat, brushing, dried brush, dip-coating, spraying, seam are coated with, whirlpool formula spraying, printing (for example, spray ink Printing), flexographic plate, extrude, spraying, intaglio plate (the style wheel shifts), static, steam deposition, fibrosis and/or silk screen printing.
It can be also can not be layer the closing of base material of non-woven base material that tackiness agent of the present invention is suitable for being used for Stretch material and another kind as location tackiness agent, core tackiness agent or elastic attachment adhesive; And be specially adapted to make goods; Comprise; But be not limited to following goods: disposable absorbent products, like diaper, adult incontinence products, mattress; Sanitary towel and other absorbent products like bib, bandage and surgery manteau or curtain, are used for absorbing liquid, like water and salt solution, and body fluid, like urine, menstruation and blood.Tackiness agent can be used to bonded nonwoven fabric or thin paper and another kind of base material or parts.Second base material can be another kind of supatex fabric, thin paper or incoherent material.The adhesive of the invention will generally be about 290
~ about 325
The temperature applied to the substrate.
As stated, absorbent structure generally will comprise supatex fabric.It is the interlocking fibrous reticulum of characteristic that supatex fabric is defined as with flexibility, porousness and globality.Each fiber that is used for forming supatex fabric can be a synthetic, naturally occurring or both combination.Each fiber can be adhered to one another with the sticking method of mechanical process, chemical method or heat.Supatex fabric has many application in industry, comprise thermal insulation, packing (for example, like the food of meat and so on), family expenses rag, surgery curtain, medical treatment clothes and disposable use goods, like diaper, adult incontinence products and sanitary towel.Thin paper is closely-related material, and each fiber can lean on also and can not be adhered to one another by chemical method therein.
Tackiness agent can be used to be connected to top layer on the bottom.Perhaps tackiness agent also can be used to be bonded to top layer or bottom on other parts of disposable use absorbent products; Like tissue layers, retaining leg, fixedly ear, band or reinforced sheet, or known generally being used for of those skilled in the art constitutes on other parts of disposable absorbent products.
Those skilled in the art is applicable to identification the material of doing top layer and bottom.Be applicable to that the typical material of making top layer is the sepage material, like the about 15～about 25g/m of basis weight
2Spunbond Vestolen PP 7052 or Vilaterm.Bottom commonly used in the disposable use absorbent products is generally processed by the liquid-impermeable material, and its effect is to be contained in liquid such as water, urine, menstruation or blood in the absorbent core of disposable absorbent products and to protect the coat of batts and/or wearer not make dirty.Be applicable to that the material of making bottom in the disposable absorbent products generally is impermeable but be permeable to steam to liquid.Instance has the liquid-impermeable material, like polyolefin film, and like Vestolen PP 7052 and Vilaterm, and gas permeable material, like the micropore polyolefin film, be referred to as ventilative film sometimes.
Tackiness agent of the present invention is specially adapted to do elasticity and connects tackiness agent.In order to make various disposable and competent goods; Like incontinence pad, disposable diapers, training pant, clothes, underwear, tSportswear, automobile decoration thing, weather strip, pad and furniture decoration etc., need the good material of tensility and elasticity.Tensility and elasticity are abilities, for example, and the characteristic that realization and wearer's body or component framework coincide.Though known have many materials that good stress-strain property and elasticity are at room temperature all arranged; But usually hoping can be at high temperature; As at body temperature or under the temperature of automotive interior in summer, during using i.e. stretching repeatedly and bouncing back, can provide and coincide or docile resilient material.This tackiness agent is particularly suitable for connecting tackiness agent as elasticity and is used for non-woven application, like baby' diaper or adult-incontinence articles.Except the city of supatex fabric outside the venue, hot melt adhesive of the present invention also is applicable to and requires to reduce packing, conversion and the bookbinding market that coating temperature keeps tackiness agent toughness and intensity simultaneously.
The matrix material that disposable elastomeric article is generally all combined with manufacturing technology by polymeric film, spandex fiber, nonwoven sheet and/or absorbent material.Spandex fiber can be with known method manufacturing, like melt-and solution-spinning and winding.Nonwoven sheet can be used manufacturings such as spun-bond process, meltblown, hy-droentanglement method, mechanical interlocking method.Film and sheet material moulding method generally all relate to known extruding and coextrusion technology, for example, blown film, casting film, abnormal shape extrude, injection-molded, extrude application and extrusion sheet moulding.Polymeric film is the liquid-impermeable material preferably, and like polyolefin film, for example, Vestolen PP 7052 and Vilaterm, and gas permeable material like the micropore polyolefin film, are referred to as ventilative film sometimes.
Durable elastomeric article like ornamental strip, clothes waistband line or belt and the building weather strip of automotive door, window, can both be used known moulding method, method for hot forming and special-shaped extrusion molding manufacturing.
When after properties of materials is to receive inclined to one side power effect, having high elastic recovery percentage (promptly low tension set percentage), generally be regarded as resilient material.The desired characteristics of resilient material is the combination of 3 temperature independent performances, i.e. stress or load is little and stress or load relaxation percentage are low during little, the strain of tension set percentage.That is to say, under low or high use temperature, should satisfy: needed stress of (1) expanded material or load are little; (2) when material is drawn, there are not or have only very little stress relaxation or load to reduce and after (3) stretch; Be after inclined to one side power or strain remove, be returned to life size fully or highly.Therefore; Elastomer polymer; If there is not thinner, be to surpass 100% and when after being stretched to its 2 times of former length and keeping 1 minute, unclamping with any curl (in fibers form) irrelevant elongation at break, reply the polymkeric substance of at least 1.5 times of its former length in 1 minute after unclamping.This base polymer includes, but not limited to tree elastomer or viton, multi-block polyurethane (comprising polyurethane-urea), like poly(ether-urethene) and poly ester urethane, polyether ester, elastomerics Vilaterm and Vestolen PP 7052, and polyetheramides.Goods of the present invention can comprise the base material that includes this type of various forms elastomer polymer, and this type base material can be used for method of the present invention, only otherwise damaging advantage of the present invention gets final product.Goods of the present invention can comprise tackiness agent and at least a elastomer substrates; Like at least a elastomeric fibre, band, film, bar, coating, ribbon and/or sheet; And comprise linear basically ethene polymers and elastomer substrates; For example; Spandex (for example; Lycra
spandex and Lycra
XA a kind ofly almost do not have on it or the spandex of unlubricated surface coating).In one embodiment, base material comprises spandex or melt-spun elastomerics.In another embodiment, base material comprise fibrous or width less than the ribbon of about 10mm natural or viton.Tackiness agent and at least a elastomer substrates can comprise at least one parts of goods, and the non-limiting example of this base part comprises waistband, the bottom bands of trouser legs, abdominal belt etc.
It is the made fiber of long-chain synthetic polymer that comprises at least 85 weight % multi-block polyurethanes that US International Trade Commission is defined as into fine material to spandex.Known Lycra
spandex has the elasticity that does not rely on temperature of near ideal, and this makes it be highly suitable for clothes, tSportswear and swim suit.
Tackiness agent embodiment of the present invention can be used as sqtructural adhesive and is used for making Stretch material, as comprise at least one deck elastomer polymer layer and at least the multilayer elastomeric layer of other layer of one deck close sheet.This type layer closes sheet and is described in, and for example, U.S. patent 5,462,708,5,733 is in 628 and 6,312,786.
The present invention also will further specify with following indefiniteness embodiment.
Embodiment
In following examples, all umbers all are that weight part and all temperature all are Fahrenheit degrees, except as otherwise noted.
The tackiness agent preparationPrescription described herein is to process in the Brabender mixing tank of 600g at the volume of band blade.Thermoplastic block copolymers and about 20% oil in the prescription add be preheating to about 325
rotating cylinder in.In case even, just add the mid-block tackifier.Add extra oil and end block tackifier at last.When mixture just stops blending technology evenly the time.
Prepare tackiness agent with following material:
Kraton MD6460 can be a kind of following segmented copolymer of forming available from Kraton Polymers U.S.: 30% vinylbenzene as the random copolymers of end block and 70% isoprene and divinyl as mid-block.Press the ISO1133 method and measure, the melt flow index of MD6460 is 6～11g/10min.The diblock percentage ratio of this polymkeric substance is about 30%.
Kraton 1162, can be the SIS segmented copolymers available from Kraton Polymers U.S..Styrene content is about 44%, presses the ISO1133 method and measures, and its MFI is 35.Diblock percentage ratio is about 0%.
Plastolyn 240, can be alpha-methyl styrene end block tackifying resins available from Eastman Chemical Company.
Escorez 5400, are the petroleum hydrocarbon resins available from Exxon, and its softening temperature is about 100 ℃.
Calsol 5550, can be MO available from Calumet Lubricants Company.
IRGANOX 1010FF can be an oxidation inhibitor available from Ciba-Geigy.
Used nonwoven substrates is the spunbond Vestolen PP 7052 that Avgol makes among the embodiment.
Used polyvinylidene film is the TXEM-244.0 embossing film that corona treatment is crossed among the embodiment, and thickness is 0.75 mil, is made by Pliant Corp..
Then tackiness agent is simulated the various tests of successful industrial application desired properties.These experimental details are following.
Melt viscosityThe melt viscosity of hot melt adhesive is measured with No. 27 mandrels on Brookfield RVT type Thermosel viscometer.
Tensile propertyThe tensile property of hot melt adhesive is thick with 0.125 inch that has 1 inch * 1 inch end reinforced sheet and 0.5 inch * 0.5 inch center gauge length part, and 2.5 inches long dumbbell-shaped specimen is measured.On Instron with the speed tension specimen of air chuck with 12 inches/min.Write down the stress-at-break and the yielding stress of tackiness agent then.
The mechanical dynamic performanceThe mechanical dynamic performance of hot melt adhesive is measured with RheometricsDynamic Mechanical Analyzer (RDA700 type), to obtain elasticity (G ') and the loss (relation of G ") modulus and temperature.This instrument is controlled with Rhios software 4.3.2 version.Sheet separation with parallel plate He the about 2mm of diameter 8mm.Install sample, be cooled to-100 ℃ approximately then, the starting time program.Sequence test heats up with 5 ℃ of modes of following the about 10s of constant temperature of every increase.The convection furnace that contains sample constantly receives nitrogen wash.Frequency remains on 10rad/s.Initial strain during on-test is 0.05% (at parallel plate outer rim place).Keep the moment of torsion that accurately can survey in the whole test with the automatic response option in the software.It is 80% that the maximum that the structure of this option allows software adds strain.The automatic response program is with the strain under each temperature increment of conditioned.If moment of torsion is lower than 200g-cm, then increase 25% of present value to strain.If moment of torsion is higher than 1200g-cm, then reduce 25% of present value to strain.Under the moment of torsion between 200～1200g-cm, keep the strain under that temperature increment constant.(G ") is calculated according to moment of torsion and strain data by software to shear energy storage or Young's modulus (G ') and shearing out-of-phase modulus.Also calculate simultaneously their ratio, i.e. G "/G ', also be called tan δ.The temperature of getting tan δ peak is the Tg of mid-block.The point of crossing temperature is G ' and the G " temperature that is equal to each other.
Creep propertiesThe method of estimating creep properties is to measure stretching condition free end elastic strip down at final application of temperature (100
) what have bounced back in following 4 hours.
Be determined at monofilament (spandex) length (" initial length ") that is bonded under the stretching condition between two nonwoven sheets or between a slice nonwoven sheet and a slice polymeric film.The two ends of cutting supatex fabric/film and spandex and measure the gained free end of fiber 100
amount of recovery in following 4 hours.Be calculated as follows the creep percentage then:
For example, be 15cm if the initial distance between the mark is a final distance between 20cm and the mark, then the creep percentage is exactly 25%.5 samples of test are on average respectively organized the result of elastic strip and are write down the result under each condition.
Embodiment 1
Make the tackiness agent sample shown in the table 1 as stated.This embodiment shows, makes elasticity be connected tackiness agent with the S-I/B-S that is less than 15% with the combination of another kind of segmented copolymer and produces good creep property.Used adhesive applicator is a Nordson Spiral sprayer.Lycra Spandex fiber with 3 620 dtexs comes cohesive polymers and nonwoven substrates.During tackiness agent coating with the non-parcel style of successive.The glue spread of these 3 bars is 8mg/ inches.Creep properties also is shown in table 1 with other performance.
Table 1
| Sample | |
| Kraton?MD?6460 | 13 |
| Kraton?1162 | 7 |
| Plastolyn?240 | 10.0 |
| Escorez?5400 | 54.0 |
| Calsol?5550 | 16.0 |
| Irgonox?1010 | 0.5 |
| Creep properties | 12.3％ |
| G ' (dyne/cm of 40 ℃ 2) | 2.6×10 5 |
| Tg(℃) | 21.0 |
| The point of crossing temperature (℃) | 82.4 |
| Ultimate tensile strength (pound/inch 2) | 191.5 |
| Yielding stress (pound/inch 2) | 24.3 |
Viscosity (centipoise, temperature (
 |
5050(300) |
Claims (20)
1. hot melt adhesive; It comprises styrene content at least 25 weight % and diblock percentage ratio less than PS-isoprene/butadiene multipolymer-polystyrene block copolymer of 30%, be not second segmented copolymer and the tackifying resin of PS-isoprene/butadiene multipolymer-polystyrene block copolymer
Wherein said hot melt adhesive comprises; Weight with adhesive compound is benchmark; 0.5 the weight %～said PS of 18 weight %-isoprene/butadiene multipolymer-polystyrene block copolymer, at the most said second segmented copolymer of 30 weight %, 30～80 weight % tackifying resins and; Randomly, 25 weight % liquid plasticizers and 25 weight % waxes at the most at the most.
2. the tackiness agent of claim 1, wherein the diblock percentage ratio of PS-isoprene/butadiene multipolymer-polystyrene block copolymer is less than 25%.
3. the tackiness agent of claim 1, wherein the diblock percentage ratio of PS-isoprene/butadiene multipolymer-polystyrene block copolymer is less than 20%.
4. the tackiness agent of claim 1 comprises the said PS of 5～18 weight %-isoprene/butadiene multipolymer-polystyrene block copolymer, said second segmented copolymer of 10～20 weight %, 30～70 weight % tackifying resins, 0～25 weight % liquid plasticizer and 0～5 weight % wax.
5. the tackiness agent of claim 1 comprises the said PS of 0.5～18 weight %-isoprene/butadiene multipolymer-polystyrene block copolymer, said second segmented copolymer of 30 weight %, 5～70 weight % tackifying resins, 0～20 weight % liquid plasticizer and 0～5 weight % wax at the most.
6. the tackiness agent of claim 1 comprises the said PS of 0.5～18 weight %-isoprene/butadiene multipolymer-polystyrene block copolymer, said second segmented copolymer of 5～20 weight %, 30～70 weight % tackifying resins, 0～20 weight % liquid plasticizer and 0～5 weight % wax.
7. the tackiness agent of claim 1, wherein said second segmented copolymer is selected from following one group: styrene-isoprene-phenylethene, styrene-butadiene-styrene, vinylbenzene-iso-butylene-vinylbenzene, styrene-ethylene/butylene-styrene block copolymer, styrene-ethylene/propylene-styrene segmented copolymer or their combination.
8. the tackiness agent of claim 7, wherein said second segmented copolymer is a styrene-butadiene-styrene.
9. the tackiness agent of claim 1, it comprises liquid plasticizer and wax simultaneously.
10. the goods that comprise the tackiness agent of claim 1.
11. the goods of claim 10 comprise elastomeric fibre or other Stretch material.
12. the goods of claim 10 comprise elastomeric fibre.
13. the goods of claim 11, it is disposable absorbing products.
14. the goods of claim 13, it is disposable elastomeric article.
15. the goods of claim 10, but to be tensile layer close sheet for it.
16. the goods of claim 13, it is a diaper.
The method of first base material and second base material 17. bond; Comprise the following step: the tackiness agent of coating claim 1 at least the first base material; Tackiness agent on making at least the second base material and being present in first base material contacts, thereby said first and second base material is bonded together.
18. the method for claim 17 is non-woven base material one of at least in wherein said first or second base material.
19. the method for claim 17 is a Stretch material one of at least in wherein said first or second base material.
20. the method for claim 17 is a spandex fiber one of at least in wherein said first or second base material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/284,102 US20070117934A1 (en) | 2005-11-21 | 2005-11-21 | Adhesive containing block copolymers |
| US11/284102 | 2005-11-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1970670A CN1970670A (en) | 2007-05-30 |
| CN1970670B true CN1970670B (en) | 2012-08-08 |
Family
ID=37708201
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006101603340A Active CN1970670B (en) | 2005-11-21 | 2006-11-16 | Adhesive containing block copolymers |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20070117934A1 (en) |
| EP (1) | EP1788058B1 (en) |
| JP (1) | JP5254542B2 (en) |
| CN (1) | CN1970670B (en) |
| CA (1) | CA2567414A1 (en) |
| ES (1) | ES2712472T3 (en) |
| PT (1) | PT1788058T (en) |
| TR (1) | TR201905031T4 (en) |
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|---|---|---|---|---|
| WO2023065311A1 (en) * | 2021-10-22 | 2023-04-27 | Henkel Ag & Co. Kgaa | Hot melt adhesive composition and use thereof |
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| CA2757877C (en) * | 2009-04-08 | 2013-08-06 | The Procter & Gamble Company | Stretchable laminates of nonwoven web(s) and elastic film |
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| US10414957B2 (en) | 2015-03-16 | 2019-09-17 | H.B. Fuller Company | Low application temperature hot melt adhesive composition |
| WO2016149385A1 (en) * | 2015-03-16 | 2016-09-22 | H.B. Fuller Company | An elastic adhesive composition and an elastic composite made with the same |
| CN108882997B (en) * | 2016-04-27 | 2022-01-11 | 金伯利-克拉克环球有限公司 | Absorbent article |
| US10814593B2 (en) | 2016-07-25 | 2020-10-27 | Avient Corporation | Super-vibration damping thermoplastic elastomer blends and articles made therewith |
| US10597562B2 (en) | 2016-08-03 | 2020-03-24 | H.B. Fuller Company | Elastic attachment hot melt adhesive composition and a disposable absorbent article made with the same |
| CN114430687A (en) * | 2019-09-23 | 2022-05-03 | 宝洁公司 | SAP-immobilization materials based on styrene block copolymers |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP1788058A3 (en) | 2007-06-13 |
| JP2007138170A (en) | 2007-06-07 |
| EP1788058B1 (en) | 2019-01-09 |
| PT1788058T (en) | 2019-02-11 |
| US20070117934A1 (en) | 2007-05-24 |
| JP5254542B2 (en) | 2013-08-07 |
| ES2712472T3 (en) | 2019-05-13 |
| CA2567414A1 (en) | 2007-05-21 |
| TR201905031T4 (en) | 2019-05-21 |
| CN1970670A (en) | 2007-05-30 |
| EP1788058A2 (en) | 2007-05-23 |
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